Patent GB-439675-A (GB)
Title: Improvements in the dyeing or printing of animal fibres
IPC: D06P1/655
Filed: 1934-03-12
Abstract: Acid wool dyes, dyeing with; printing.--Animal fibrous materials, e.g. wool, silk, hair or leather or mixed fabrics of animal and non-animal fibres are dyed or printed with acid dyestuffs with the aid of water-soluble substances, free from sulphonic groups and capable of forming salts with the dyestuffs, which contain at least one basic reacting atom of pentavalent phosphorus or tetravalent sulphur and at least one aromatic radicle or at least one aliphatic radicle with at least 6 carbon atoms, such substances being used either in a pretreatment of the material or during the dyeing or printing.  In the dyeing process lower amounts of acid than usual and temperatures below boiling may be employed.  Specified phosphorus and sulphur compounds are trimethyloctylphosphonium hydroxide, triethylcetyl- or triethyldodecyl-phosphonium bromide, dimethyloctodecylsulphonium hydroxide, dipropylaurylsulphonium bromide and methylethylcetylsulphonium hydroxide or its methylsulphuric acid salt.  The pretreatment may be effected with aqueous solutions of the compounds or with solutions thereof in organic solvents such as ethyl alcohol, acetone or carbon tetrachloride.  Wetting agents, protective colloids, water-soluble organic solvents, &c. may also be present in the pretreatment liquor or the dyebath, suitable additions being, e.g., turkey red oil, sulphonated higher aliphatic alcohols, sulphonic acids, condensation products from high molecular carboxylic acids and hydroxy or amino-alkylsulphonic acids or albumen degradation products, alkylated aromatic sulphonic acids or salts thereof, reaction products of alkylene oxides on hydroxy, amino or carboxylic compounds, ethyl alcohol, ethyleneglycol ethers, polyglycol ethers, polyglycerols, polymerized ethylene oxide, pyridine, alkali metal phosphates, alkalies, waterglass and hydroxyalkylamines.  Preparations suitable for dissolving to form a dyebath may be made up containing the dyestuff and the phosphorus or sulphur compound with or without a dispersing agent or protective colloid, dextrin, Glaubers's salt or common salt. The following examples are specified: (1) wool is treated for 1 hour in a bath at 50 DEG  C. containing triethyldodecylphosphonium bromide or the methylsulphuric acid salt of methylethylcetyl sulphonium hydroxide and then dyed a deep red in a bath containing the complex chromium compound of the dyestuff, 4-chloro-2-aminophenol-6-sulphonic acid --> 2 : 4-dihydroxyquinoline and sulphuric acid; instead of pretreating the wool, methylethylcetylsulphonium hydroxide may be added to the dyebath. (2) Worsted wool is dyed a deep green, fast to rubbing, in a bath containing Amids black-green B, the methylsulphuric acid salt of methylethylcetylsulphonium hydroxide, Glauber's salt and acetic acid, the bath being heated to boiling in \ba1/2\be hour, whereupon formic acid is added and boiling is continued for 1 hour; the dyestuff may be replaced by Acid violet 6BN; alternatively the wool may be pretreated for \ba1/2\be hour with a solution at 30 DEG  C. of the sulphonium compound and dyed in the usual manner. Trimethyloctylphosphonium hydroxide is obtained by reacting trimethylphosphine with octyl iodide and converting the iodide into the hydroxide.  Triethylcetyl- and triethyldodecyl-phosphonium bromides are obtained by reacting triethylphosphine with cetyl and dodecyl bromides respectively.  Dimethyloctodecylsulphonium hydroxide is obtained by reacting dimethyl thioether with octodecyl iodide and converting the iodide into the hydroxide.  Dipropyllaurylsulphonium bromide is obtained by reacting dipropyl thioether with lauryl bromide.  Methylethylcetylsulphonium hydroxide is obtained by reacting methylethyl thioether with cetyl iodide and converting the iodide into the hydroxide.